This invention relates to cosmetic product, especially antiperspirant and/or deodorant products which contain an antiperspirant active ingredient and which provides better efficacy and stability without compromising aesthetics. The compositions are emulsions made with an external (or oil) phase and an internal phase which contains the active ingredient. These emulsions may be used to form gel, soft solid or roll-on products.
A large variety of antiperspirant and/or deodorant formulations have been described in the patent literature and/or have been made commercially available. These products have included suspension as well as emulsions. Also various physical forms may be used such as solids (for example, wax and gel sticks), semi-solids (for example, gels and creams), liquids (for example, roll-on products) and sprays (both aerosol and non-aerosol).
In recent years a strong emphasis has been placed on improving both the performance of antiperspirant and/or deodorants, for example, the efficacy, aesthetics, and stability of these products. One of the particular problems is trying to obtain an emulsion product that has efficacy comparable to suspension products. A second problem is the stabilization of emulsion products to achieve a product that is shelf stable, but which releases an active ingredient in a timely manner. These problems have been caused, in part, by the use of non-volatile silicones used to match the refractive index of the two phases for clear systems or used for improving skin feel. The use of such non-volatile silicones (1) decreases the ability of the active ingredient to be released from the composition thereby decreasing efficacy, and (2) makes the emulsions so stable that the active is not released in a timely manner.
With regard to emulsions, U.S. Pat. No. 4,673,570 to Soldati describes uniform, clear gelled antiperspirant compositions, free of waxes wherein the emulsions comprise in combination a volatile silicone fluid, a silicone emulsifier (such as a mixture of cyclomethicone and dimethicone copolyol), a destabilizing auxiliary emulsifier, water, a non-volatile emollient (such as C10-C20 alkyl fatty esters and ethers), linear silicone fluids, a coupling agent (such as low molecular weight alcohols and glycols), an active antiperspirant component and other ancillary agents.
U.S. Pat. No. 5,008,103 to Raleigh et al describes water-in-oil antiperspirant emulsions having a discontinuous polar phase containing water and optionally containing an emulsifier with a hydrophilic-lipophilic balance (HLB value) greater than 8, and a volatile silicone continuous phase with a dimethicone copolyol emulsifier. The HLB parameter is a well known parameter the calculation of which is disclosed and explained in numerous references. For nonionic surfactants, data obtained by actual analysis is usually a more accurate measure of HLB values (rather than theoretical determinations). U.S. Pat. No. 5,401,870 to Raleigh et al and to U.S. Pat. No. 5,292,503 to Pereira et al describe similar subject matter.
U.S. Pat. No. 5,216,033 to Pereira et al describes a transparent water-in-oil emulsion containing a silicone phase with a dimethicone copolyol and an aqueous phase containing a refractive index xe2x80x9ctransparency structurantxe2x80x9d to produce a refractive index matched clear emulsion. The transparency structurant is a C3-C8 polyhydric alcohol.
U.S. Pat. No. 5,599,533 to Stepniewski et al describes the use of silicone elastomer in an aqueous water-in-oil emulsion, but does not describe a clear emulsion.
U.S. Pat. No. 5,989,531 describes a liquid composition made with (a) an active phase comprising a selected glycol, a nonionic emulsifier having an HLB value greater than 8 and an antiperspirant and/or deodorant active; and (b) a silicone phase made with one or more of a dimethicone copolyols having an HLB less than 7 and nonionic emulsifiers having an HLB greater than 7, wherein the silicone phase has at least 10% silicone and the ratio of the silicone phase to he active phase is in the range of 1:1-1:4. Optional ingredients include the use of non-volatile silicones, volatile silicones and organic emollients.
U.S. Pat. No. 6,033,651 describes a single phase aqueous gel composition comprising 0.05-50% of a polysaccharide gellant, and 1-30% of an antiperspirant active ingredient solubilized in the aqueous single phase wherein the composition is formed with a water and an oil emulsion comprising a gelled aqueous phase comprising a polysaccharide gellant and an antiperspirant active ingredient solubilized in the aqueous single phase; and an oil phase.
Historically, suspension products such as sticks have exhibited better efficacy than emulsion products. Previous attempts have not successfully overcome the problems of improving efficacy and achieving satisfactory formation of emulsions. Thus, it is an object of this invention to provide improved anhydrous emulsions which exhibit improved efficacy which efficacy is comparable to that achieved in suspension products and, at the same time, have a stability profile that allows for satisfactory stability on the shelf. Another issue is the formation of emulsions which are stable on the shelf but which destabilize sufficiently after application to a skin surface so as to release an efficacious amount of an active ingredient. Thus, it is an object of the present invention to provide emulsions with those characteristics. It is also an object of this invention to provide gel or soft solid compositions which can, if desired, be formed into clear compositions. It is still another object of this invention to provide compositions that can, if desired, be formed into clear compositions without the use of microemulsions
This invention relates to an anhydrous cosmetic composition comprising:
(a) 15-33% of an external phase (also called the oil phase) which is made with at least one selected naphthalate organic ester; a volatile silicone based emulsifier; and a volatile silicone; and
(b) 67-85% of an internal phase which is made with an active ingredient, such as an antiperspirant active, in a solvent (especially a glycol or polyglycol solvent) wherein the conductance of the composition is at least 250, particularly 300, more particularly 400 and especially 500 micro Siemens at a loading of at least 7% by weight level of antiperspirant active as measured by the test described below.
For the external phase all or a major portion of what would have been a non-volatile silicone component has been replaced by the naphthalate ester. While a dimethicone copolyol is still included, the use of this particular naphthalate ester obviates the need for the use of any other non-ionic emulsifiers. Also, while small amounts (for example, 0-5%) of a non-volatile silicone may be included, it is preferred that the compositions be made without the addition of non-volatile silicones.
The emulsions of this invention comprise an external and an internal phase as described below:
External Phase comprising
(a) 0.1-25% (particularly 0.5-25% and more particularly 2.5-15%) of an organic naphthalate ester (especially 2,6-di-(ethylhexyl)naphthalate having a refractive index in the range of 1.43-1.60, which is not soluble in alcohol or glycols (except in minor amounts such as up to 1.0%)and which is capable of releasing an antiperspirant active to achieve a specified conductivity,
(b) a sufficient amount of a silicone copolyol to achieve a solids content of 0.25-10% (particularly 1.0-3.0%) wherein the silicone copolyol may be added with or without solvent;
(c) a sufficient amount of a volatile silicone (for example, a cyclomethicone such as a D5 cyclomethicone) to achieve a quantum sufficient (xe2x80x9cq.s.xe2x80x9d) amount of the external phase as 15-33% (for example, wherein part of the volatile silicone may be added in a silicone copolyol which itself is obtained already mixed with a volatile silicone as a solvent, such as a 40-48% dimethicone copolyol in cyclomethicone);
(d) 0-5% of a silicone elastomer (on an actives basis); and
(e) 0-15%, particularly 0-10% and, more particularly, 0-5% of at least one emollient;
Internal Phase comprising
(a) 0.1-30% (particularly 0.1-25%, and more particularly 10-20%) of an antiperspirant active (on an anhydrous basis); and
(b) a sufficient amount of a solvent component to dissolve the cosmetically active ingredient and to complete the internal phase (for example, a glycol component to dissolve an antiperspirant active), with a maximum amount being about 70% of solvent for a deodorant product and abut 80% for an antiperspirant product; wherein the ratio of the external phase to the internal phase is in the range of 1:1-1:4 and all amounts are in percent by weight based on the total weight of the composition.
Additionally, other optional ingredients can be added to the internal phase such as 0-10% of an alcohol such as ethanol, 0-5% fragrance, and 0-5% of a non-ionic emulsifier.
Particular compositions include (a) a composition wherein the internal phase comprises up to 7% antiperspirant active and 50-80% glycol component; and (b) a composition wherein the internal phase comprises 7-25% of an antiperspirant active and 35-55% of a glycol component.
Optionally, one or more of each of fragrance, color, preservative can be added to the appropriate phase as is known to those skilled in the art.
In general the organic naphthalate esters can be described as a monoester, diester and/or polyester of a naphthalene dicarboxylic acid and which are reaction products of
(i) a naphthalene dicarboxylic acid having the structure: HO2Cxe2x80x94Qxe2x80x94CO2H where Q is a naphthalene; and
(ii) an alcohol having the structure R1xe2x80x94OH, or a diol having the structure HOxe2x80x94R2xe2x80x94OH, or a polyglycol having the structure HOxe2x80x94R3xe2x80x94(xe2x80x94Oxe2x80x94R2xe2x80x94)mxe2x80x94OH, wherein R1 is an alkyl group, straight chain or branched, having 1 to 22 carbon atoms, R2 and R3, may be the same or different, and are each an alkylene group, having 1 to 6 carbon atoms, and wherein m and n are each 1 to about 100, preferably 1 to about 10, more preferably 2 to about 7, or a mixture thereof.
A diester of the present invention has the structure: R1O2Cxe2x80x94Qxe2x80x94CO2R1 wherein R1 and Q have the same meanings as defined above.
The diesters and polyesters of naphthalene dicarboxylic acids that are of interest include those of the following Formula I:
HOxe2x80x94[xe2x80x94R3xe2x80x94O2Cxe2x80x94Qxe2x80x94CO2xe2x80x94]nxe2x80x94R2xe2x80x94OHxe2x80x83xe2x80x83Formula I
wherein R2 and R3, may be the same or different, are each an alkylene group having 1 to 6 carbon atoms, and n=1 to about 100, preferably 1 to about 10, more preferably 2 to about 7.
Alternatively, the diesters and polyesters used in the present invention can be end-capped with an alcohol or an acid. The end-capped polyesters have a Formula II:
R1xe2x80x94O2Cxe2x80x94Qxe2x80x94CO2xe2x80x94[R2xe2x80x94O2Cxe2x80x94Qxe2x80x94CO2xe2x80x94]nxe2x80x94R4xe2x80x83xe2x80x83Formula II
wherein R1 and R2 and n are as defined above, with reference to Formula (I) and R4 is independently selected from the same group as defined for R1 in Formula I.
The preferred diesters and polyesters of the present invention have a weight average molecular weight of about 244 to about 4000, and more preferably about 450 to about 1500. To achieve the full advantage of the present invention, the diester or polyester has a weight average molecular weight of about 500 to about 1000.
The naphthalene dicarboxylic acid is selected from the group consisting of
1,2-naphthalene dicarboxylic acid; 1,3-naphthalene dicarboxylic acid;
1,4-naphthalene dicarboxylic acid; 1,5-naphthalene dicarboxylic acid;
1,6-naphthalene dicarboxylic acid; 1,7-naphthalene dicarboxylic acid;
1,8-naphthalene dicarboxylic acid; 2,3-naphthalene dicarboxylic acid;
2,6-naphthalene dicarboxylic acid; 2,7-naphthalene dicarboxylic acid, and
mixtures thereof. Preferred dicarboxylic acids are the 2,6-, 1,5- and
1,8-naphthalene dicarboxylic acids.
The alcohol R1xe2x80x94OH can be, for example, methanol, ethanol, propanol, isopropyl alcohol, n-butanol, sec-butanol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol, 1-hexanol, 1-octanol, 1-decanol, isodecyl alcohol, 1-undecanol, 1-dodecanol, 1-tridecyl alcohol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1-eicosonol, 1-decosonol, 2-ethylhexyl alcohol, 2-butyloctanol, 2-butyldecanol, 2-hexyldecanol, 2-octyldecanol, 2-hexyldodecanol, 2-octyldodecanol, 2-decyltetradecanol, and mixtures thereof.
The glycol component is at least one member selected from the group consisting of glycols and polyglycol such as, for example, ethylene glycol, propylene glycol, 1,2-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, methyl propanediol, 1,6-hexanediol, 1,3-butanediol, 1,4-butanediol, PEG-4 through PEG-100, PPG-9 through PPG-34, pentylene glycol, neopentyl glycol, trimethylpropanediol, 1,4-cyclohexanedimethanol, 2,2-dirnethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and mixtures thereof.
Optionally up to 75% of the naphthalate portion of the composition can be substituted by an emollient selected from the group consisting of:
(a) fats and oils which are the glyceryl esters of fatty acids, or triglycerides, normally found in animal and plant tissues, including those which have been hydrogenated to reduce or eliminate unsaturation. Also included are synthetically prepared esters of glycerin and fatty acids. Isolated and purified fatty acids can be esterified with glycerin to yield mono-, di-, and triglycerides. These are relatively pure fats which differ only slightly from the fats and oils found in nature. The general structure may be represented by Formula VI: 
xe2x80x83wherein each of R21, R22, and R23 may be the same or different and have a carbon chain length (saturated or unsaturated) of 7 to 30. Specific examples include peanut oil, sesame oil, avocado oil, coconut, cocoa butter, almond oil, safflower oil, corn oil, cotton seed oil, castor oil, hydrogenated castor oil, olive oil, jojoba oil, cod liver oil, palm oil, soybean oil, wheat germ oil, linseed oil, and sunflower seed oil.
(b) hydrocarbons which are a group of compounds containing only carbon and hydrogen. These are derived from petrochemicals. Their structures can vary widely and include aliphatic, alicyclic and aromatic compounds. Specific examples include paraffin, petrolatum, hydrogenated polyisobutene, and mineral oil.
(c) esters which chemically, are the covalent compounds formed between acids and alcohols. Esters can be formed from almost all acids (carboxylic and inorganic) and any alcohol. Esters here include those derived from carboxylic acids and an alcohol. The general structure would be R40COxe2x80x94OR50. The total number of carbons for R40 and R50 together can vary from 7 to 50 (particularly 14-30) and can be saturated or unsaturated, straight chained or branched. Other esters of interest include certain benzoates, fumarates, and esters with glycol portions or alkoxylated portions. Specific examples include isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl isostearate, butyl stearate, octyl stearate, hexyl laurate, cetyl stearate, diisopropyl adipate, isodecyl oleate, diisopropyl sebacate, isostearyl lactate, C12-15 alkyl benzoates, myreth-3 myristate, dioctyl malate, neopentyl glycol diheptanoate, dipropylene glycol dibenzoate, C2-15 alcohols lactate, isohexyl decanoate, isohexyl caprate, diethylene glycol dioctanoate, octyl isononanoate, isodecyl octanoate, diethylene glycol diisononanoate, isononyl isononanoate, isostearyl isostearate, behenyl behenate, C12-15 alkyl fumarate, laureth-2 benzoate, octyldodecyl myristate, cetyl ricinoleate, myristyl myristate,
(d) adipic acid blends selected from the group consisting of trimethyl pentanediol/adipic acid copolymer (LEXOREZ TL8 from Inolex, Philadelphia, Pa.); trimethyl pentanediol/adipic acid/isononanoic acid copolymer (LEXOREZ TC8); and adipic acid/diethylene glycol/glycerin crosspolymer (LEXOREZ 100).
(e) lanolin and its derivatives which are a complex esterified mixture of high molecular weight esters of (hydroxylated) fatty acids with aliphatic and alicyclic alcohols and sterols as well as propoxylated and/or butoxylated species. Specific examples include lanolin, lanolin oil, lanolin wax, lanolin alcohols, lanolin fatty acids, isopropyl lanolate, propoxylated lanolin, butoxylated lanolin, and acetylated lanolin alcohols.
(f) mixtures and blends of two or more of the foregoing.
Particular examples of emollients for the silicone phase include organic emollients selected from: (1) propoxylated alcohols such as PPG-3 myristyl ether and PPG-14 butyl ether; (2) fats and oils such as avocado oil and mink oil; (3) hydrocarbons such as mineral oil, isoparaffins, hydrogenated polyisobutene, and squalane, particularly straight or branched chain hydrocarbons having 10-35 carbons; (4) lanolin and lanolin derivatives such as lanolin, lanolin oil; and (5) fatty esters such as isopropyl myristate, C12-15 alkyl benzoate, dioctyl adipate, and octylmethoxycinnamate.
The emollient or emollient mixture or blend thereof incorporated in compositions according to the present invention can, illustratively, be included in amounts of 0-15%, particularly 1-10%, more particularly 1-5% and, even more particularly, 2-3% by weight, based on the total weight of the composition.
For the silicone copolyols, dimethicone copolyols are of special interest. The dimethicone copolyols are of various types. These include copolyols of the following Formulae IA and IIA. Formula I materials may be represented by:
(R10)3xe2x80x94SiOxe2x80x94[(R11)2xe2x80x94SiO]xxe2x80x94[Si(R12)(Rbxe2x80x94Oxe2x80x94(C2H4O)pxe2x80x94(C3H6O)sxe2x80x94Rc)O]yxe2x80x94Sixe2x80x94(R13)3xe2x80x83xe2x80x83Formula IA
wherein each of R10, R11, R12 and R13 may be the same or different and each is selected from the group consisting of C1-C6 alkyl; Rb is the radical xe2x80x94CmH2mxe2x80x94; Rc is a terminating radical which can be hydrogen, an alkyl group of one to six carbon atoms, an ester group such as acyl, or an aryl group such as phenyl; m has a value of two to eight; p and s have values such that the oxyalkylene segment xe2x80x94(C2H4O)pxe2x80x94(C3H6O)sxe2x80x94 has a molecular weight in the range of 200 to 5,000; the segment preferably having fifty to one hundred mole percent of oxyethylene units xe2x80x94(C2H4O)pxe2x80x94 and one to fifty mole percent of oxypropylene units xe2x80x94(C3H6O)sxe2x80x94; x has a value of 8 to 400; and y has a value of 2 to 40. Preferably each of R10, R11, R12 and R13 is a methyl group; Rc is H; m is preferably three or four whereby the group Rb is most preferably the radical xe2x80x94(CH2)3xe2x80x94; and the values of p and s are such as to provide a molecular weight of the oxyalkylene segment xe2x80x94(C2H4O)pxe2x80x94(C3H6O)sxe2x80x94 of between about 1,000 to 3,000. Most preferably p and s should each have a value of about 18 to 28.
A second siloxane polyether (copolyol) has the Formula IIA:
(R10)3xe2x80x94SiOxe2x80x94[(R11)2xe2x80x94SiO]xxe2x80x94[Si(R12)(Rbxe2x80x94Oxe2x80x94(C2H4O)pxe2x80x94Rc)O]yxe2x80x94Sixe2x80x94(R13)3xe2x80x83xe2x80x83Formula IIA
wherein p has a value of 6 to 16; x has a value of 6 to 100; and y has a value of 1 to 20 and the other moieties have the same definition as defined in Formula I.
It should be understood that in both Formulas I and II shown above, that the siloxane-oxyalkylene copolymers of the present invention may, in alternate embodiments, take the form of endblocked polyethers in which the linking group Rb, the oxyalkylene segments, and the terminating radical Rc occupy positions bonded to the ends of the siloxane chain, rather than being bonded to a silicon atom in the siloxane chain. Thus, one or more of the R10, R11, R12 and R13 substituents which are attached to the two terminal silicon atoms at the end of the siloxane chain can be substituted with the segment xe2x80x94Rbxe2x80x94Oxe2x80x94(C2H4O)pxe2x80x94(C3H6O)sxe2x80x94Rc or with the segment xe2x80x94Rbxe2x80x94Oxe2x80x94(C2H4O)pxe2x80x94Rc. In some instances, it may be desirable to provide the segment xe2x80x94Rbxe2x80x94Oxe2x80x94(C2H4O)pxe2x80x94(C3H6O)sxe2x80x94Rc or the segment xe2x80x94Rbxe2x80x94Oxe2x80x94(C2H4O)pxe2x80x94Rc at locations which are in the siloxane chain as well as at locations at one or both of the siloxane chain ends.
Particular examples of suitable dimethicone copolyols are available either commercially or experimentally from a variety of suppliers including Dow Corning Corporation, Midland, Mich.; General Electric Company, Waterford, N.Y.; Witco Corp., Greenwich, Conn.; and Goldschmidt Chemical Corporation, Hopewell, Va. Examples of specific products include DOW CORNING(copyright) 5225C from Dow Corning which is a 10% dimethicone copolyol in cyclomethicone; DOW CORNING(copyright) 2-5185C which is a 45-49% dimethicone copolyol in cyclomethicone; SILWET L-7622 from Witco; ABIL EM97 from Goldschmidt which is a 85% dimethicone copolyol in D5 cyclomethicone; and various dimethicone copolyols available either commercially or in the literature.
It should also be noted that various concentrations of the dimethicone copolyols in cyclomethicone can be used. While a concentration of 10% in cyclomethicone is frequently seen commercially, other concentrations can be made by stripping off the cyclomethicone or adding additional cyclomethicone. The higher concentration materials such as DOW CORNING(copyright) 2-5185 material is of particular interest.
By volatile silicone material is meant a material that has a measurable vapor pressure at ambient temperature. For the volatile silicone portion, examples of volatile silicones (particularly silicones with a boiling point of 250 degrees C. or less at atmospheric pressure) include cyclomethicone (especially cyclopentasiloxane, also called xe2x80x9cD5xe2x80x9d), xe2x80x9chexamethyldisiloxanexe2x80x9d, and low viscosity dimethicone (for example, Dow Coming(copyright) 200 fluid having a viscosity of 1-200 centistokes). Such volatile silicones include conventional cyclic and linear volatile silicones Illustratively, and not by way of limitation, the volatile silicones are one or more members selected from the group consisting of cyclic polydimethylsiloxanes such as those represented by Formula Formula III: 
where n is an integer with a value of 3-7, particularly 5-6. For example, DC-245 fluid (or the DC-345 version) from Dow Corning Corporation (Midland, Mich.) is a type of cyclomethicone which can be used. These include a tetramer (or octylmethylcyclotetrasiloxane) and a pentamer (or decamethylcyclopentasiloxane). The volatile linear silicones can also be included in this group of volatile silicones and are one or more members selected from the group consisting of linear polydimethylsiloxanes such as those represented by Formula IV: 
and t is selected to obtain a viscosity of 1-200 centistokes.
It is also possible to include a silicone elastomer in the external phase. Suitable elastomers include those described in copending PCT case WO 99/51192, incorporated by reference herein. Particular examples of suitable elastomers are SFE 167, a cetearyl dimethicone/vinyl dimethicone crosspolymer from GE Silicones (Waterford, N.Y.); SFE168, a cyclomethicone (and) dimethicone/vinyl dimethicone crosspolymer from GE Silicones; vinyl dimethicone crosspolymers such as those available from Shin Etsu Silicones of America (Akron, Ohio) under trade names KSG-15 (cyclomethicone (and) dimethicone/vinyl dimethicone crosspolymer), KSG-16 (dimethicone (and) dimethicone/vinyl dimrethicone crosspolymer), KSG-17 (cyclomethicone (and) dimethicone/vinyl dimethicone crosspolymer), KSG-18 (phenyl trimethicone (and) dimethicone/phenyl vinyl dimethicone crosspolymer); and KSG-20 (dimethicone copolyol crosspolymer; dimethicone/vinyl dimethicone crosspolymer from Dow Coming Corporation (Midland, Mich.) under trade name Dow Corning 9506 Cosmetic Powder; and a mixture of cyclomethicone and stearyl-vinyl/hydromethylsiloxane copolymer available from Grant Industries, Inc. (Elmwood Park, N.J.) under the trade name Gransil SR-CYC.
For the antiperspirant active used in the active phase various antiperspirant active materials that can be utilized according to the present invention provided that they are soluble at a suitable concentration in the active phase. These include conventional aluminum and aluminum/zirconium salts, as well as aluminum/zirconium salts complexed with a neutral amino acid such as glycine, as known in the art. See each of European Patent Application Number. 512,770 A1 and PCT case WO 92/19221, the contents of each of which are incorporated herein by reference in their entirety, for disclosure of antiperspirant active materials. The antiperspirant active materials disclosed therein, including the acidic antiperspirant materials, can be incorporated in the compositions of the present invention if they are soluble in the active phase. Suitable materials include (but are not limited to) aluminum chlorides (various types including, for example, anhydrous form, hydrated form, etc.), zirconyl hydroxychlorides, zirconyl oxychlorides, basic aluminum chlorides, basic aluminum chlorides combined with zirconyl oxychlorides and hydroxychlorides, and organic complexes of each of basic aluminum chlorides with or without zirconyl oxychlorides and hydroxychlorides and mixtures of any of the foregoing. These include, by way of example (and not of a limiting nature), aluminum chlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, aluminum chlorohydrol-propylene glycol complex, zirconyl hydroxychloride, aluminum-zirconium glycine complex (for example, aluminum zirconium trichlorohydrex gly, aluminum zirconium pentachlorohydrex gly, aluminum zirconium tetrachlorohydrex gly and aluminum zirconium octochlorohydrex gly), aluminum dichiorohydrate, aluminum chlorohydrex PG, aluminum chlorohydrex PEG, aluminum dichlorohydrex PG, aluminum dichlorohydrex PEG, aluminum zirconium trichlorohydrex gly propylene glycol complex, aluminum zirconium trichlorohydrex gly dipropylene glycol complex, aluminum zirconium tetrachlorohydrex gly propylene glycol complex, aluminum zirconium tetrachlorohydrex gly dipropylene glycol complex, and mixtures of any of the foregoing. The aluminum-containing materials can be commonly referred to as antiperspirant active aluminum salts. Generally, the foregoing metal antiperspirant active materials are antiperspirant active metal salts. In the embodiments which are antiperspirant compositions according to the present invention, such compositions need not include aluminum-containing metal salts, and can include other antiperspirant active materials, including other antiperspirant active metal salts. Generally, Category I active antiperspirant ingredients listed in the Food and Drug Administration""s Monograph on antiperspirant drugs for over-the-counter human use can be used. In addition, any new drug, not listed in the Monograph, such as tin or titanium salts used alone or in combination with aluminum compounds (for example, aluminum-stannous chlorohydrates), aluminum nitratohydrate and its combination with zirconyl hydroxychlorides and nitrates, can be incorporated as an antiperspirant active ingredient in antiperspirant compositions according to the present invention. Preferred antiperspirant actives that can be incorporated in the compositions of the present invention include the enhanced efficacy aluminum salts and the enhanced efficacy aluminum/zirconium salt-glycine materials, having enhanced efficacy due to improved molecular distribution, known in the art and discussed, for example, in PCT No. WO92/19221, the contents of which are incorporated by reference in their entirety herein.
Antiperspirant actives can be incorporated into compositions according to the present invention in amounts in the range of 0.1-30% (on an anhydrous, solids basis), particularly 0.1-25%, preferably 5-25%, wherein the amounts are percent by weight based on the total weight of the composition. The amount used will depend on the formulation of the composition. For example, at amounts in the lower end of the broader range (for example, 0.1-5%), the antiperspirant active material will not substantially reduce the flow of perspiration, but will reduce malodor, for example, by acting as a deodorant material. Compositions made with amounts of active in the higher end of the range (for example, 9-25%) will be considered antiperspirants.
One type of active is selected from the group consisting of Westchlor A2Z4105 from Westwood Chemicals (Middletown, N.Y.) wherein the active material is a 28-35% concentration of active in propylene glycol in a 30:70 phase ratio. This active material may be used in amounts as high as 20-24% in the final cosmetic composition. In these formulations with a higher active level, the organic phase can be maintained at a higher level of up to 45%.
Deodorant active materials can be selected from several types of materials:
(a) lesser amounts of antiperspirant actives, such as in the range of 0.1-5.0 percent by weight based on the total weight of the composition;
(b) fragrances, such as in the range of 0.5-3.0 percent by weight based on the total weight of the composition;
(c) effective amounts of antimicrobial agents, for example, 0.05-5.0 percent (particularly 0.1-1% and, more particularly, 0.25-1.0%) by weight based on the total weight of the composition; examples include bacteriostatic quaternary ammonium compounds (such as cetyl trimethyl-ammonium bromide, and cetyl pyridinium chloride), 2,4,4xe2x80x2-trichloro-2xe2x80x2-hydroxydiphenylether (Triclosan), N-(4-chlorophenyl)-Nxe2x80x2-(3,4-dichlorophenyl)urea (Triclocarban), silver halides, octoxyglycerin (SENSIVA(trademark) SC 50) and various zinc salts (for example, zinc ricinoleate). Triclosan or Triclocarban can, illustratively, be included in an amount of from 0.05% to about 0.5% by weight, of the total weight of the composition.
The glycol or polyglycol is selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, methyl propanediol, 1,6-hexanediol, 1,3-butanediol, 1,4-butanediol, PEG-4 through PEG-100, PPG-9 through PPG-34, pentylene glycol, neopentyl glycol, trimethylpropanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 2,2,4,4-tetramethyl-1,3 -cyclobutanediol, and mixtures thereof. More particular examples of the glycol component include one or more members of the group consisting of propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, methyl propylene glycol, low molecular weight (less than 600) polyethylene glycol, low molecular weight (less than 600) polypropylene glycols, and mixtures of any of the foregoing. Propylene glycol is of particular interest because the antiperspirant active is more soluble in this type of glycol. Tripropylene glycol has lower irritancy, but the antiperspirant active is not as soluble in this glycol. Mixtures of glycols may be used to balance these desirable properties.
The compositions of the present invention can include other optional ingredients to improve the aesthetics and/or performance of the cosmetic compositions of the invention. These include colorants, fillers, fragrances, emollients, masking agents, etc. Such one or more other optional ingredients can be added to the internal or external phases or both in appropriate amounts. For example, fragrances will frequently be partitioned to both the external and internal phases regardless of when or to what phase (or final product) the fragrance is added.
While the mechanism of why this invention provides improved efficacy is not completely understood, it is believed that the invention solves two problems. The first problem is the barrier problem which is caused, in significant part, by the presence of a non-volatile silicone component. The second problem is the stability of the emulsion which, if too stable, results in failure of the antiperspirant to be released and a reduction in efficacy. This invention overcomes both of these problems with (a) the significant reduction or, preferably, total elimination of the non-volatile silicone component that is frequently used in antiperspirant and/or deodorant products and (b) the creation of emulsion that exhibit satisfactory stability on the shelf and yet break down when applied to the skin to release the antiperspirant active allow for improved performance. As an additional benefit, the formulations of this invention may be made as clear products without the use of microemulsions.
The release of antiperspirant actives into the sweat is a significant event in the development of an antiperspirant effect. The magnitude of the antiperspirant effect is related to the concentration of the antiperspirant salt in the sweat, and therefore measuring the concentration of antiperspirant salt can provide an estimate of antiperspirant efficacy. A variety of methods can be used to evaluate antiperspirant salt concentration, ranging from atomic absorption, ICP, and HPLC to solution conductance of aqueous films. The later method is especially well suited for measuring the release of small amounts of antiperspirant salts. The methods outlined below use solution conductance to estimate antiperspirant salt release upon short exposures to deionized water.
As noted above, the conductance of the compositions of the invention is defined with reference to a value of at least 250 micro Siemens/cm/ml when the composition is loaded with at least 7% of an antiperspirant active (such as the antiperspirant actives listed above) and when the conductance is measured by a fixed geometry test. For purposes of clarification is should be explained that there are a variety of tests and test conditions that can be used to evaluate:
(1) xe2x80x9cConductancexe2x80x9d is defined as an absolute measure of current flow through a solution with the dimensions of micro Siemens/cm, which value is independent of probe geometry. This value is divided by the volume (in ml) of applied water to give the conductance number with the units of micro Siemens/cm/ml. This test is deemed a more reproducible measurement since it references a set of fixed dimensions and units.
(2) Alternatively, xe2x80x9cconductivityxe2x80x9d as a measure of current flow through a solution without reference to probe geometry, and which is measured in micro Siemens. This test is convenient for quick screening of solutions.
Standard Test for Thin Film Conductivity
One test for conductivity is called herein the xe2x80x9cstandardxe2x80x9d test. A non-conducting plastic block (for example, made from PLEXIGLAS(copyright) material) to form an oral shaped well 12.2 cmxc3x972.5 cm with a depth of 100 microns. This depth corresponds to the mean thickness of an antiperspirant product applied to the underarm of a human person during real use conditions (approximately 50 to 100 microns). An aliquot of test sample is placed in the well of the block sufficient to fill the well to the brim. Excess sample is scraped off by running a flat edged instrument over the surface of the block. The sample block, with the product film, is then either (a) equilibrated at room temperature for two hours or (b) placed in a synthetic underarm to simulate in vivo conditions. If method (b) is used, the air temperature inside the synthetic underarm is maintained at 33 to 35xc2x0 C. and a relative humidity of 85 to 95%, and the sample blocks are placed on a temperature controlled surface maintained at body temperature (37xc2x0 C.). These conditions closely approximate the temperature gradients normally found in the underarm. Samples are equilibrated in either the (a) or (b) environments for two hours prior to measurement of antiperspirant salt release by solution conductivity. After two hours the sample blocks are removed from the controlled environment and placed on a stage for conductivity measurement. An aliquot of 250 microliters of water with a resistance of at least 17 mega Ohms is placed on the surface of the sample film, and the conductance of the water is measured as a function of time with a Skicon 200 Skin surface Hygrometer (I.B.S. Co., Ltd., Shizuoka-ken, 430, Japan) using an Elsnau (MT-8Probe) electrode (Todd Maibach and Associates, San Francisco, Calif.). The electrode is positioned so that it touches the bottom of the test sample in the well. Conductivity is measured in micro Siemens at 3.5 MHz. Data is collected at 0.1 sec intervals for approximately 100 sec. Solution conductivity after 10 seconds of exposure to the water is used to compare the release of active salt for different formulations This method is believed to be particularly useful for evaluating the release of antiperspirant salts in the absence of other salts. The standard method is useful as a quick screening tool for active salt release studies. A solution conductivity of approximately 400 or greater micro Siemens at 10 sec after application of the water droplet to the surface of the test sample, can be considered evidence of significant release of the antiperspirant active salt from the film surface and correlates with improved antiperspirant efficacy.
Fixed Geometry Test for Thin Film Conductance
One of the limitations of the Standard Test is that the area of the water droplet is not controlled and, therefore, the apparent conductance (which is measured as conductivity because the water volume is not controlled) is dependent on droplet spreading. This will lead to an underestimate of the actual solution conductance (and therefore antiperspirant salt release), of water drops which spread significantly. In order to measure the absolute concentration of the antiperspirant salts the spreading of the water drop must be stopped. This can be accomplished by placing a well of know dimensions on the surface of the product film to establish an area of constant size that is exposed to the water droplet. A more predictable test is needed, such as the Fixed Geometry Test.
The Fixed Geometry Test uses the same basic technique as the Standard Test in terms of preparation of the test well, addition of the test sample and equilibration of the sample to a selected temperature. Instead of allowing the water to flow freely on the surface of the test film, however, a second structure of non-conducing plastic predrilled with holes of a fixed diameter is clamped over the well block. The second structure with holes is also made of a non-conducting material (such as PLEXIGLAS material), is open on both ends and has an internal diameter of 1.905 cm. The bottom of each predrilled hole is fitted with a small O-ring to prevent leakage of the water. A 400 microliter aliquot of water (rather than the 250 microliter aliquot used in the Standard Test) with a resistance of 17 mega Ohms is then placed in the hole to cover the test sample. This will normally result in a liquid height for water of about 1.4 mm. The Elsnau probe is positioned through the drilled hole so that the bottom of the probe rests on the bottom of the well at a right angle. Because of the fixed shape, data can be obtained as conductance in micro Siemens/cm/ml using the method described for calculation.
As will be appreciated by those skilled in the art, a variety of other shapes, sizes and orientations of electrodes can be used. In another variation on the Fixed Geometry Test, thin gold wires (99% purity, set of 2, each about 1 mm in diameter) can be constructed to be in parallel with the surface of the water (and covered by the water) and conductance can be measured.
The electrode used in both types of tests must be calibrated so that a conductivity in micro Siemens can be obtained. Such calibration with a salt solutions in water of known conductance is known to those skilled in the art.
While different readings can be obtained depending on the thickness of the films, the test used, etc. it is important to establish a standard test for purposes of defining conductivity according to this invention. The Fixed Geometry Test is set as the defining test because it is believed to be more reproducible. Thus a minimum conductance value of 250 micro Siemens/cm/ml is the lower limit. Interestingly, minimum values for the Standard Test seemed to run about 400 micro Siemens due to the way the test was conducted. For the data described here, samples should be placed in a chamber at the humidity and elevated temperature conditions described above for about 2 hours. Samples not subjected to elevated temperatures should give higher values.
An average efficacy gel having a water contest of greater than 35%(such as Gillette""s Right Guard Antiperspirant Gel) was compared with an improved gel made according to Example 3, below. The average efficacy gel has a standard conductivity of 295xc2x135 micro Siemens at 10 seconds and a fixed geometry conductivity of 121xc2x147 micro Siemens/cm/ml at 10 seconds. The improved formulation made according to this invention had a standard conductivity of 1884xc2x1225 micro Siemens at 10 seconds and a fixed geometry conductance of 1213xc2x143 micro Siemens/cm/ml at 10 seconds. The improved formulation was ranked as above average in efficacy in a clinical test whereas the average gel was ranked as average in efficacy in a clinical test.
While it is not known precisely how the compositions of this invention work, it has been observed that they have a combination of two important properties. These compositions exhibit superior stability on the shelf and yet degrade on contact with the skin to release the active ingredient with a higher level of efficacy than is usually achieved. The deodorant and/or antiperspirant compositions disclosed in this invention form metastable emulsions when deposited on the skin. The decomposition of these emulsions upon application can be assessed by the thin film conductance method described herein. In another test the superiority of this invention is evaluated by applying test on skin, waiting 30 minutes and examining the product film under the microscope. Comparison to another formulations containing an antiperspirant active of low efficacy shows that the emulsions of effective formulations break up on the skin while the emulsions of the low efficacy samples remain intact.
Particular formulations of interest include:
Formulation A
External Phase comprising
(a) 3.0-15% of 2,6-di-(ethylhexyl)naphthalate;
(b) 1.5-3.0% of a 48% dimethicone copolyol in cyclomethicone or 0.1-7% (particularly 2-5%) of a 40% dimethicone copolyol in cyclomethicone);
(c) 4.0-16% of a volatile silicone (for example, a cyclomethicone such as a D5 cyclomethicone); and
(d) 0-1% of a silicone elastomer.
Internal Phase comprising
(a) 9.0-20% of an antiperspirant active (on an anhydrous basis); and
(b) a sufficient amount (35-55%) of a glycol component to dissolve the antiperspirant active and complete the internal phase; wherein the ratio of the external phase to the internal phase is in the range of 1:1-1:4.
Formulation B
External Phase comprising
(a) 10-15% of 2,6-di-(ethylhexyl)naphthalate;
(b) 2-3% of a 40% dimethicone copolyol in cyclomethicone; and
(c) 8-10% of a volatile silicone (for example, a cyclomethicone such as a D5 cyclomethicone).
Internal Phase comprising
(a) 12-15% of an antiperspirant active (on an anhydrous basis); and
(b) a sufficient amount (30-39%) of a glycol component to dissolve the antiperspirant active and complete the internal phase; wherein the ratio of the external phase to the internal phase is in the range of 1:1-1:4.
Formulation C
External Phase comprising
(a) 3-6% of 2,6-di-(ethylhexyl)naphthalate;
(b) 3-6 of a C12-15 alkyl benzoate;
(c) 15-18% of a 10% dimethicone copolyol in cyclomethicone; and
(d) 0-1% of a volatile silicone (for example, a cyclomethicone such as a D5 cyclomethicone).
Internal Phase comprising
(a) 12-15% of an antiperspirant active (on an anhydrous basis); and
(b) a sufficient amount (35-55%) of a glycol component to dissolve the antiperspirant active and complete the internal phase; wherein the ratio of the external phase to the internal phase is in the range of 1:1-1:4.
Formulation D
External Phase comprising
(a) 8-12% of 2,6-di-(ethylhexyl)naphthalate;
(b) 18-22% of a 10% dimethicone copolyol in cyclomethicone; and
(c) 0-1% of a volatile silicone (for example, a cyclomethicone such as a D5 cyclomethicone).
Internal Phase comprising
(a) 15-20% of an antiperspirant active (on an anhydrous basis); and
(b) a sufficient amount of a glycol component (35-55%) to dissolve the antiperspirant active and complete the internal phase; wherein the ratio of the external phase to the internal phase is in the range of 1:1-1:4.
Formulation E
External Phase comprising
(a) 4-8% of an organic naphthalate ester (especially 2,6-di-(ethylhexyl)naphthalate);
(b) 4-8% hydrogenated polyisobutene;
(c) 4-8%of a 40% dimethicone copolyol in cyclomethicone; and
(c) 6-10% of a volatile silicone (for example, a cyclomethicone such as a D5 cyclomethicone).
Internal Phase comprising
(a) 15-20% of an antiperspirant active (on an anhydrous basis); and
(b) a sufficient amount of a glycol component (for example, 35-55) to dissolve the antiperspirant active and complete the internal phase;
wherein the ratio of the external phase to the internal phase is in the range of 1:1-1:4.
Compositions of the present invention may be made by the techniques described in the Examples below. In general, the external and internal phases are formed separately using heating with the addition of a non-ionic emulsifier as needed. The alcohol component is added to the internal phase. The internal phase is added to the external phase very slowly. After the addition has been completed, the mixture is stirred at speeds on the order of 500-1000 rpm (for example, 1000 rpm), to achieve a homogeneous mixture, followed by homogenization at speeds which are correlated with a voltage setting of about 55-70, particularly 60, on a Powerstat Variable Autotransformer to achieve the target viscosity. Compositions with a viscosity of 0-50,000 centipoise, especially 5,000-20,000 centipoise, may be suitable for roll-on products while compositions having a viscosity on the order of 50-400,000 centipoise may be more suitable for soft solids or creams.
A variety of equipment and techniques may be used to obtain the compositions of the invention, including one pass homogenization, colloidal mill. Examples of such equipment include Sonic Production Sonolator 200-30, and Sonic Tri-Homo Colloid Mill both of which may be obtained from Sonic Corporation, Stratford, Conn.
It is believed that the more homogeneous the composition is and the more uniform the particle size, the better properties of the composition.
The cosmetic composition according to the present invention can be packaged in conventional containers, using conventional techniques. Where a gel, cream or soft-solid cosmetic composition is produced, the composition can be introduced into a dispensing package (for example, conventional packages for gels with glide on applicators, jars where the gel or cream is applied by hand, and newer style packages having a top surface with pores) as conventionally done in the art. Thereafter, the product can be dispensed from the dispensing package as conventionally done in the art, to deposit the active material, for example, on the skin. For roll-ons the compositions can be placed in a conventional type of container. This provides good deposition of the active material on the skin.
Throughout the present specification, where compositions are described as including or comprising specific components or materials, or where methods are described as including or comprising specific steps, it is contemplated by the inventors that the compositions of the present invention also consist essentially of, or consist of, the recited components or materials, and also consist essentially of, or consist of, the recited steps. Accordingly, throughout the present disclosure any described composition of the present invention can consist essentially of, or consist of, the recited components or materials, and any described method of the present invention can consist essentially of, or consist of, the recited steps.
Throughout the specification and claims all percents are in percents by weight based on the entire composition unless otherwise stated.
Compositions of the present invention can be formulated as clear, translucent or opaque products, although clear products are preferred. A desired feature of the present invention is that a clear, or transparent, cosmetic composition, (for example, a clear or transparent deodorant or antiperspirant composition) can be provided. The term clear or transparent according to the present invention is intended to connote its usual dictionary definition; thus, a clear, gel antiperspirant composition of the present invention allows ready viewing of objects behind it. By contrast, a translucent composition, although allowing light to pass through, causes the light to be scattered so that it will be impossible to see clearly objects behind the translucent composition. An opaque composition does not allow light to pass therethrough. Within the context of the present invention, a gel or liquid is deemed to be transparent or clear if the maximum transmittance of light of any wavelength in the range 400-800 nm through a sample 1 cm thick is at least 35%, preferably at least 50%. The gel or liquid is deemed translucent if the maximum transmittance of such light through the sample is between 2% and less than 35%. A gel or liquid is deemed opaque if the maximum transmittance of light is less than 2%. The transmittance can be measured by placing a sample of the aforementioned thickness into a light beam of a spectrophotometer whose working range includes the visible spectrum, such as a Bausch and Lomb Spectronic 88 Spectrophotometer. As to this definition of clear, see European Patent Application Publication No. 291,334 A2. Thus, according to the present invention, there are differences between transparent (clear), translucent and opaque compositions.